JPH03208046A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To speed up the decoloration during the development processing of the photosensitive material by using specific dyes. CONSTITUTION:This photosensitive material is provided with a hydrophilic colloidal layer (e.g.: protective layer) contg. >=1 kinds of the dyes expressed by formula as fine particle dispersed bodies. In the formula, R1, R2 denote alkyl or aryl, etc.; R3, R4 denote H, alkyl, etc.; L1 to L3 denote methine; n denotes 0 or 1 and carboxyl, sulfonic acid aryl amide or phenolic hydroxyl groups are combined within the molecule. The more specific examples of these dyes include compds. or the like in which R1 in the formula is -C6H4-OH; R2 is -C6H4-OH; R2 is -O-CH3; R4 is p-N(CH3)2; L1 is =CH-; n is 0.

Description

Detailed Description of the Invention (Industrial Application Field) The present invention relates to a silver halide photographic light-sensitive material having a dyed hydrophilic colloid layer, which is photochemically inert and easy to apply in the photographic processing process. The present invention relates to a silver halide photographic material having a decolorizing button and/or a hydrophilic colloid layer containing a dye to be eluted.

(Prior Art) In silver halide photographic light-sensitive materials, photographic emulsion layers and other hydrophilic colloid layers are often colored for the purpose of absorbing light in a specific wavelength range.

When it is necessary to control the spectral composition of light incident on the photographic emulsion layer, a colored layer is usually provided on the side farther from the support than the photographic emulsion layer. Such a colored layer is called a filter layer. When there are multiple photographic emulsion layers, a filter layer may be located between them.

An image based on the fact that light scattered during or after passing through a photographic emulsion layer is reflected at the interface between the emulsion layer and the support, or at the surface of the light-sensitive material opposite to the emulsion layer, and enters the photographic emulsion again. For the purpose of preventing blurring or halation, colored eyebrows called antihalation eyebrows are provided between the photographic emulsion layer and the support, or on the surface of the support opposite to the photographic emulsion layer. If there are multiple photographic emulsion eyebrows, an antihalation layer may be placed between the layers.

Decrease in image sharpness due to scattering of light in the photographic emulsion layer (this phenomenon is generally called imaginary)
To prevent this, the photographic emulsion layer is also colored. These hydrophilic colloid layers to be colored usually contain a dye. This dye needs to satisfy the following conditions.

(11. Must have appropriate spectral absorption according to the purpose of use.

(2) Photochemically inert. That is, the performance of the silver halide photographic emulsion layer should not be adversely affected in a chemical sense, such as a decrease in sensitivity, latent image regression, fog or fog.

(3) It must not be bleached during the photographic processing process, or be eluted into the casing, processing solution, or washing water, leaving any harmful coloring on the photographic material after processing.

(4) Do not diffuse from the dyed layer to other layers.

(5) It has excellent stability over time in solutions or photographic materials and does not change color or fade.

In particular, when the colored layer is a filter layer or an antihalation layer placed on the same side of the support as the photographic emulsion layer, those layers are selectively colored and the other layers are colored. In many cases, it is necessary to ensure that the

This is because, otherwise, not only will it have a harmful spectral effect on other debris, but its effectiveness as a filter layer or antihalation eyebrow will be diminished. However, when the dyed layer and other hydrophilic colloid eyebrows come into wet contact, it often occurs that some of the dye diffuses from the former to the latter. Many efforts have been made in the past to prevent such dye diffusion.

For example, a method in which a hydrophilic polymer with a charge opposite to that of a dissociated anionic dye is made to coexist in a layer as a mordant and the dye is localized in a specific eyebrow area through interaction with dye molecules is disclosed in the US patent λ,! ψl,! Buφ No., same, /211
, No. 31, 3.62, Bu? It is disclosed in No. φ etc.

In addition, a method of dyeing a specific layer using a water-insoluble dye solid is disclosed in JP-A-12435P, Ibid. r! -/r
! No. 310, same! J-/! ! Jjl No. 3-27r
JI, 43-/F7F4'j, Kotako 7l on the same evening
No. 7, European Patent/Jtθ/ No. 7! No. 4, same λ
7ψ7JJ issue, 27zjjj issue, same Kotatada 3! issue,
It is disclosed in world patents rt7o da7de ψ, etc.

In addition, a method for dyeing specific eyebrows using metal salt fine particles to which a dye has been adsorbed is disclosed in U.S. Patent No. 2,7/Y, Orr;
Da2bu. tdal No. 1, same co. Gudebu, t←No.3, JP-A-4
0−ψ! It is disclosed in Ko J7, etc.

However, even with these improved methods, the speed of decolorization during development processing is slow, and changes in various factors such as speeding up processing, improving processing solution composition, or improving photographic emulsion composition are required. In this case, there was a problem that the decolorizing function could not always be fully exhibited.

(Problems to be Solved by the Invention) Therefore, an object of the present invention is to create a solid fine particle dispersion designed to dye a specific hydrophilic colloid layer in a photographic light-sensitive material and rapidly decolorize it during development. An object of the present invention is to provide a photographic material containing a dye.

(Means for Solving the Problems) /) The object of the present invention is to provide a silver halide photographic light-sensitive material having hydrophilic colloid waste containing at least one compound represented by the following general formula (I) as a solid fine particle dispersion. achieved.

General formula (■) (In the formula, each of R1 and R2ti is an alkyl group, tfcF'i
represents an aryl group, R3 and R4 each represent a hydrogen atom, an alkyl group, a hydroxyl group, an alkoxy group, or an amino group; L1
, L2, Latj: each represents a methine group, n FiO
t9 represents l. However, the compound represented by general formula (I) has at least one carboxyl group, sulfonic acid arylamide group, or phenolic hydroxyl group in the molecule. ) C) The object of the present invention is to contain at least one compound represented by general formula (1) as solid-dispersed fine particles, and at least one compound represented by the following general formula (II) as solid-dispersed fine particles. It is achieved by silver halide photographic light-sensitive materials containing silver halide.

General formula (ff) (wherein, R5 is a hydrogen atom, an alkyl group, an aryl group, a cyano group, a hydroxyl group, -COOR7, -CONR7R8, -B7, -NHCOR7t- Table L, each of R6, an alkyl group, an aryl group Represents Lll, L12, L13, L
14.L 15 ij each represents a methine group, p. q represents 01 or l. However, the compound represented by general formula (II) has at least one carboxyl group, sulfonic acid arylamide group, or phenolic hydroxyl group in the molecule. ) Next, the compound represented by the general formula (1) will be explained in detail.

The alkyl group represented by R1 and R2 is an unsubstituted alkyl group (eg, methyl, ethyl, n-propyl, isopropyl, cyclohexyl). tta-substituted alkyl group {
As a substituent, phenyl group (e.g. ehazhenzyl, carboxybenzyl, hydroxybenzyl), carboxyl group (
For example, carboxymethyl, carboxyethyl, cocarboxyethyl) are preferred, and R1% and R2 may be the same or different.

The aryl group represented by R1 and R2 is an unsubstituted aryl group (e.g. phenyl), a substituted aryl group {a halogen atom as a substituent (e.g. dichloro7enyl, x, t
-cyclophenyl), alkyl groups (e.g. ←-methylphenyl), hydroxyl groups (e.g. hydroxyphenyl), carboxyl groups (e.g. carboxy7enyl, J,!
-Cical f: xyphenyl), sulfonic acid amide group (e.g., l'φ-methanesulfonylaminophenyl), alkoxy group (e.g., ψ-methoxyphenyls"cλ-hydroxyethoxy7enyl)), amino group (e.g.,
N-dimethylaminophenyl! -(N-carboxymethyl-N-ethylamino)phenyl), ester group (e.g. μ-ethoxycarbonylphenyl Ll'cH sulfonic acid ester group (e.g. ψ-methanesulfonyloxyphenyl) 1 preferred, Rl, R2i -t may be the same or different.

The alkyl group represented by R3 and R4 is an unsubstituted alkyl group (for example, methyl, ethyl, normalprovil, improvil, cyclohexyl), a mono- or substituted alkyl group {
Examples of substituents include phenyl groups (e.g., tifbenzyl, carboxybenzyl, hydroxybenzyl), carboxyl groups (e.g., carboxymethyl, l-carboxyethyl,
cocarboxyethyl), ester groups (eg, ethoxycarbonylmethyl, coacetoxyethyl)} are preferred.

In the alkoxy group represented by R3 and R4, the alkyl portion thereof is an unsubstituted alkyl group (for example, methyl, ethyl,
normal propyl, isopropyl, cyclohexyl),
! or a substituted alkyl group {as a substituent, a phenyl group (e.g. benzyl, carboxybenzyl, hydroxybenzyl), a carboxyl group (e.g. carboxymethyl, /monocarboxyethyl, 2-carboxyethyl), an ester group (e.g. ethoxycarbonylmethyl, coacetoxyethyl)}.

The amine group represented by R3 and R4 may be any of an unsubstituted amino group, an alkylamino group, a box, or a dialkylamino group, and the alkyl portion thereof may be an unsubstituted alkyl group (for example, methyl, ethyl, normal propyl, isopropyl, cyclohexyl), casing or substituted alkyl group {
Examples of substituents include phenyl groups (e.g., benzyl, carboxybenzyl, hydroxybenzyl), carboxyl groups (e.g., carboxymethyl, carboxyethyl,
An amino group having an ester group (eg, ethoxycarbonylmethyl, coacetoxyethyl)} is preferable.

The substituents represented by R3 and R4 may be the same or different.

Methine groups represented by L1, L2, and L3 are preferred, and < is an unsubstituted methine group, but substituents (for example, methyl, ethyl,
7 enyl).

It is npaOmatapa/.

The compound represented by general formula (I) has at least one group selected from a carboxyl group, a sulfonic acid arylamide group, and a phenolic hydroxyl group.

Next, the compound represented by the general formula (fl) will be explained in detail.

The alkyl groups represented by R5, R6, R7, and R8 are unsubstituted alkyl groups (e.g., methyl, ethyl, n-propyl, isopropyl, cyclohexyl), casings, or substituted alkyl groups {with halogen atoms as substituents (e.g., Cochloroethyl, /, /, 2, Cotetrafluoroethyl),
7-enyl group (e.g. benzyl, carboxybenzyl),
Hydroxyl group (e.g. hydroxyethyl, 3-hydroxypropyl), alkoxy group (e.g. 2-methoxyethyl, J-(J-hydroxyethoxy)ethyl), carboxyl group (e.g. carboxymethyl, /-carboxyethyl, 2-carboxy ethyl), sulfonic acid amide group (
For example, methanesulfonamide ethyl), amino groups (for example J-(N,N dimethylaminoethyl), esters (
e.g. ethoxycarbonylmethyl, acetoxyethyl)
} is good.

The aryl group represented by R5, R6, R7, and R8 is an unsubstituted aryl group (for example, phenyl), a casing or a substituted aryl group {a halogen atom (fPIJlφ-chloroa as a substituent)
7-enyl, λ, j-cycloO phenyl), alkyl groups (e.g. ψ-methyl 7-enyl), water ffi groups (e.g. hydroxyphenyl), carboxyl groups (e.g. carboxy 7-enyl, 3,!-dicarboxy) phenyl),
sulfonic acid amide group (fFIJ, tbap-methanesulfonylaminophenyl, l-sul7amoyl phenyl),
Alkoxy group (e.g., l≠-methoxyphenyl, φ1 (
(cohydroxyethoxyphenyl), amino groups (e.g. N.N-dimethylaminophenyl, u-(N-carboxymethyl-N-ethylamino), phenyl), esters (e.g. tbal-ethoxycarbonylphenyl, ←−(λ
-hydroxyethoxyphenyl),! or a sulfonic acid ester group (for example, φ-methanesulfonyloxyphenyl)}.

The methine groups represented by L11, L12, L13, L14, and L15 are preferred, and 〈 is an unsubstituted methine group, but the substituent (
For example, methyl, ethyl, phenyl).

Among the compounds represented by the general formula (II), those which do not have a sulfo group, a sulfo group, or a salt of a carboxyl group as a substituent are particularly preferred.

Further, among the compounds represented by the general formula (II), preferred are those having at least two groups selected from a carboxyl group, a sulfonic acid amide group, a phenolic hydroxyl group, and a phenolic hydroxyl group.

Next, specific examples of the compounds represented by the general formulas (1) and (II) of the present invention will be shown, but the present invention is not limited thereto.

The compound represented by general formula (1) is Heterocyclic Compounds, Vo
l. ．． 2 0; John Wiley & Son
s: New York, London, /942.

On the other hand, the compound represented by the general formula (II) is l, Kodi-substituted virazolidine-3,! -It can be easily synthesized by a condensation reaction between diones and the corresponding dialdehyde dianyl hydrochloride. Also,/,! -Disubstituted virazolidine-3. ! - Diones are Heterocyclic Compounds, V
ol. 2 0; John Wiley & Son
s: New York, London, /9t2.

The compound of general formula (1) or Fi(II) is used in an amount of /-/000 mg per m2 of area on the photosensitive material, preferably l-t00rng per m2.

When using the compound of general formula (1) or (I) as a filter dye or antihalation dye, any effective amount can be used, provided that the optical density is 0. No OJ Les J. It is best to use it within the range of j. The addition time may be at some stage before coating.

The compound of general formula (I') or Fi(II) according to the present invention can be used in both emulsion layers and other hydrophilic colloid layers.

The fine particle dispersion of the compound of general formula (1) or Fi(II) of the present invention can be prepared by a method of precipitating the compound of the present invention in the form of a dispersion, and/or by a known pulverization method in the presence of a dispersant.
For example, ball milling (ball mill, vibrating ball mill,
It can be formed by a method such as planetary ball milling, sand milling, colloid milling, jet milling, roller milling, etc. (in which case, a solvent (for example, water, alcohol, etc.) may be present). Alternatively, after dissolving the compound of the present invention in a suitable solvent, a poor solvent for the compound of the present invention may be added to precipitate a microcrystalline powder. In that case, a dispersing surfactant may be used. good. Alternatively, the compound of the present invention may be completely dissolved by controlling the pH, and then microcrystallized by changing the pH. The microcrystalline particles of the compound of the present invention in the dispersion have an average particle size of 1θμm or less, more preferably 2μm or less, and particularly preferably have an average particle diameter of 0! It is more preferable that the particles be microparticles with a particle diameter of .mu.m or less, and in some cases, a particle size of 0.1 llm or less.

Seratin is a typical hydrophilic colloid, but any other conventionally known colloid used for photography can be used.

The silver halide emulsions used in the present invention are preferably silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide and silver chloride.

The silver halide grains used in the present invention may have regular crystal shapes such as cubic or octahedral, or irregular crystal shapes such as spherical or plate-like.
gular) crystal form, or a composite form of these crystal forms. It is also possible to use a mixture of particles of various crystal forms, but it is preferable to use regular crystal forms.

The silver halide grains used in the present invention may have different phases inside and on the surface, or may consist of a uniform phase. Also, particles (
For example, the emulsion may be a negative type emulsion), or it may be a grain mainly formed inside the grain (for example, an internal latent image type emulsion, a prefogged direct reversal type emulsion). Preferably,
These are particles on which a latent image is formed primarily on the surface.

The silver halide emulsion used in the present invention has a thickness of 0.5
The diameter is preferably 0.3 microns or less, preferably 0.3 microns or less. A tabular grain emulsion in which grains of 6 microns or more and an average aspect ratio of 5 or more account for 50% or more of the total projected area, or a tabular grain emulsion with a statistical coefficient of variation (expressed as the diameter of a circular approximation of the projected area) In terms of distribution, a monodisperse emulsion having a value S/d (standard deviation S divided by diameter d) of 20% or less is preferred. Further, two or more kinds of tabular grain emulsions and monodispersed emulsions may be mixed.

The photographic emulsion used in the present invention is B. Grafchides (P
, Glafkides), Chimie er Physique Photography (Chimie er Phys.
ique Pho-tographique) (Ballmontel, 1967) G.F. Duffin (
G. F. Duffin), Photographic
Emulsion chemistry (Pho-tograph
ic Emulsion Chemistry) (
Focal Press, 1966), V. L. Zelikman et al., Making and Coating Photographic Emulsions (Making and Coating Photographic Emulsions)
It can be prepared using the method described in "Photographic Emulsion" (Focal Press, 1964).

In addition, during the formation of silver halide grains, silver halide additives such as ammonia, rhodanpotash, rhodanammonium, and thioether compounds (e.g., U.S. Pat. No. 3,271,157, U.S. Pat. No. 3,574) are used to control grain growth. , No. 628, No. 3,704,130, No. 4,297.439, No. 4,276,374, etc.), thione compounds (e.g., JP-A No. 144319/1983)
No. 5 3-8 2 4 0 8, No. 55-777
No. 37, etc.), amine compounds (e.g., JP-A No. 54-10
No. 0717, etc.) can be used.

In the process of silver halide grain formation or physical ripening,
A cadmium salt, a zinc salt, a thallium salt, an iridium salt or a complex salt thereof, a rhodium salt or a complex salt thereof, an iron salt or an iron complex salt, etc. may be present together.

As the binder or protective colloid that can be used in the emulsion layer or intermediate layer of the light-sensitive material of the present invention, it is advantageous to use gelatin, but other hydrophilic colloids can also be used. For example, seratin derivatives, graft polymers of seratin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, and cellulose sulfate esters; sugar derivatives such as sodium alginate and starch derivatives; polyvinyl alcohol Various synthetic hydrophilic polymeric materials can be used, such as single or copolymers of polyvinyl alcohol partial acetal, polyN-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, etc. can.

As for gelatin, there are general-purpose lime-processed gelatin, acid-processed gelatin, and Bull.Soc.
．． Sci. Photo. Japan), No.
Enzyme-treated seratin as described in J. I. 6, p. 30 (1966) may be used, or a hydrolyzate of seratin may be used.

In the photographic material of the present invention, an inorganic or organic hardening agent may be contained in any hydrophilic colloid layer constituting the photographic light-sensitive layer or the back layer. Specific examples include chromium salts, aldehydes (formaldehyde, glyoxal, glutaraldehyde, etc.), and N-methylol compounds (simethylol urea, etc.). Active halogen compound (2,4-dichloro-6-human pheasant-1,3
, 5-triazine and its sodium salt) and active vinyl compounds (1,3-bisvinylsulfonyl-2-
Propanol, 1,2-bis(vinylsulfonylacetamido)ethane, bis(vinylsulfonylmethyl)ether, vinyl polymers with vinylsulfonyl groups in their side chains, etc.) quickly harden hydrophilic colloids such as gelatin and provide stable photographic properties. This is preferable because it gives N-carbamoylpyridinium salts ((1-mol polycarbonyl-3-pyricinio) methanesulfonate, etc.) and haloamicinium salts (1-(]monol-pyricinomethylene)pyrrolidinium, 2-naphthalenesulfonate, etc.) Excellent fast curing speed.

The silver halide photographic emulsion used in the present invention may be spectrally sensitized with methine dyes or the like. Dyes that can be used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes, and hemioxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes, and complex merocyanine dyes. Any of the nuclei commonly used for cyanine dyes can be used as the basic heterocyclic nucleus for these dyes. That is, pyrroline nucleus, oxazoline nucleus, thiazoline nucleus, pyrrole nucleus, oxazole nucleus,
Thiazole nucleus, selenazole nucleus, imidazole nucleus, tetrazole nucleus, pyridine nucleus, etc. Nuclei in which an alicyclic hydrocarbon ring is fused to these nuclei: and a nucleus in which an aromatic hydrocarbon ring is fused to these nuclei, that is, indolenine Nuclei, henzintrenine nucleus, indole nucleus, henzoxazole nucleus, naphthoxazole nucleus, penzothiazole nucleus, naphthothiazole nucleus, penzoselenazole nucleus, penzimidazole nucleus, quinoline nucleus, etc. can be applied. These nuclei may have substituents on carbon atoms.

Merocyanine dyes or composite merocyanine dyes include a core with a ketomethylene structure such as a birazoline-5-one nucleus, a thiohydantoin nucleus, a 2-thioxazolidine-2,
A 5- to 6-membered heterocyclic nucleus such as a 4-dione nucleus, a thiazolidine-2,4-sion nucleus, a rhodanine nucleus, and a thiobarbituric acid nucleus can be applied.

These sensitizing dyes may be used alone or in combination, and combinations of sensitizing dyes are often used particularly for the purpose of supersensitization. Along with the sensitizing dye, the emulsion may contain a dye that itself does not have a spectral sensitizing effect or a substance that does not substantially absorb visible light and exhibits supersensitization. For example, aminostilbene compounds which are substituted nitrogen-containing heterocyclic ring groups (e.g., U.S. Pat. No. 2,933,390, U.S. Pat. No. 3,635,721)
(described in US Pat. No. 3,743,510), aromatic organic acid formaldehyde condensates (such as those described in U.S. Pat. No. 3,743,510), catmium salts, asaindene compounds, and the like. U.S. Patent No. 3,615,613, U.S. Patent No. 3,61
No. 5,641, No. 3,617,295, No. 3,635
, 721 are particularly useful.

The silver halide photographic emulsion used in this technology is used to prevent fog during the manufacturing process, storage, or photographic processing of light-sensitive materials, or to stabilize photographic performance.
Various compounds can be included. That is, azoles such as penzothiazolium salts, nitroindazoles, nitropenzimidazoles, chloropenzimidazoles, promobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptohenzimidazoles, mercaptothianazoles. , aminotriazoles, penzotriazoles,
Nitrohenzotriazoles, mercaptotetrazoles (especially 1-phenyl 5-mercaptotetrazole), etc.: mercaptopyrimicins; mercaptotriazines, thioketo compounds such as oxadorinthion,
Azaindenes, such as triazaindenes, tetraazaindenes, especially 4-hydroxy substituted (1,3.3a
, 7) tetraasaindenes), pentaasaindenes, etc.; many compounds known as antifoggants or stabilizers such as henchiosulfonic acid, pensensesulfinic acid, pensensesulfonic acid amide, etc. You can add something.

The photosensitive material of the present invention contains one or more surfactants for various purposes such as a coating aid, antistatic properties, improved slipperiness, emulsification and dispersion, prevention of adhesion, and improvement of photographic properties (for example, development acceleration, high contrast, and sensitization). But that's fine.

The light-sensitive materials made using the present invention may contain water-soluble dyes in the hydrophilic colloid layer as filter dyes or for illumination or antihalation purposes and other various purposes.

As such dyes, oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, anthraquinone dyes, and azo dyes are preferably used, and in addition, cyanine dyes, azomethine dyes, triarylmethane dyes, and lidocyanine dyes are also useful. It is. An oil-soluble dye can also be emulsified by an oil-in-water dispersion method and added to the hydrophilic colloid layer.

The invention is applicable to multilayer, multicolor photographic materials having at least two different spectral sensitivities on the support.

Multilayer natural color photographic materials usually have at least one red-sensitive emulsion layer, one green-sensitive emulsion layer and one blue-sensitive emulsion layer on a support. The arrangement order of these layers can be arbitrarily selected as necessary. A preferred layer arrangement is, from the support side, a red-sensitive layer, a green-sensitive layer and a blue-sensitive layer in that order, a blue-sensitive layer, a green-sensitive layer and a red-sensitive layer in that order, or a blue-sensitive layer, a red-sensitive layer and a green-sensitive layer in that order. Further, any emulsion layer having the same color sensitivity may be composed of two or more emulsion layers having different sensitivities to improve the ultimate sensitivity.
The layer structure may further improve the graininess.

Furthermore, a non-photosensitive layer may be present between two or more emulsion layers having the same color sensitivity. A configuration may also be adopted in which emulsion layers of different color sensitivity are inserted between emulsion layers of the same color sensitivity. A reflective layer made of fine grain silver halide or the like may be provided under the high-sensitivity layer, particularly the high-sensitivity blue-sensitive layer, to improve sensitivity.

Generally, the red-sensitive emulsion layer contains a cyan type or coupler, the green-sensitive emulsion layer contains a magenta-forming coupler, and the blue-sensitive emulsion layer contains a yellow type or coupler, but different combinations may be used depending on the case. can. For example, it may be used in combination with an infrared-sensitive layer for pseudo-color image quality or semiconductor laser exposure.

In the photographic light-sensitive material of the present invention, the photographic emulsion layer and other layers are formed on flexible supports such as plastic films, paper, and cloth, or rigid supports such as glass, ceramic, and metal, which are commonly used in photographic light-sensitive materials. applied. Useful as flexible supports are films of semi-synthetic or synthetic polymers such as cellulose nitrate, cellulose acetate, cellulose acetate butyrate, polystyrene, polyvinyl chloride, polyethylene terephthalate, polycarbonate, baryta layers or alpha-olefins. Paper coated with or laminated with a polymer (eg, polyethylene, polypropylene, ethylene/butene copolymer), etc.

The support may be colored using dyes or pigments.

It may be made black for the purpose of blocking light. The surface of these supports is generally treated with an undercoat to improve adhesion to photographic emulsion layers and the like. The support surface is coated before or after priming.
Glow discharge, corona discharge, ultraviolet irradiation, flame treatment, etc. may also be applied.

Various known coating methods such as dip coating, roller coating, curtain coating, and extrusion coating can be used to coat the photographic emulsion layer and other hydrophilic colloid layers. U.S. Patent No. 268 129 as appropriate
4, 2761791, 3526528 and 3508947, etc., multiple layers may be applied simultaneously.

The present invention can be applied to various color and black and white photosensitive materials. Typical examples include color negative film for general use or movies, color reversal film for slides or television, color paper, color positive film, color reversal paper, color diffusion transfer type photosensitive materials, and heat developable color photosensitive materials. can. Research Disclosure, No. 17123
(July 1978), or U.S. Pat. No. 4,126,46.
The present invention can also be applied to black-and-white photosensitive materials for X-rays and the like by using the black color-forming couplers described in British Patent No. 1 and British Patent No. 2,102,136. Films for plate making such as lithium film or scanner film,
The present invention is also applicable to X-ray films for direct and indirect medical use or industrial use, negative black and white films for photography, black and white photographic paper, COM or ordinary microfilms, silver salt diffusion transfer type photosensitive materials and printout type photosensitive materials. can.

When the photographic element of the present invention is applied to color diffusion transfer photography, it may be of the peel-apart (beer-apart) type or
-16356, 48-33697, JP-A-50-13040 and British Patent No. 1,330,524
Integrated as described in the issue.
It is possible to adopt a structure of a film unit that does not require peeling as described in Japanese Patent Application Laid-Open No. 57-119345.

The use of a polymeric acid layer protected by a neutralizing timing layer in either type of format described above is advantageous in increasing processing temperature latitude. When used in color diffusion transfer photography, it may be added to any layer in the sensitive material, or it may be sealed in a processing solution container as a developer component.

Various exposure means can be used for the photosensitive material of the present invention. Any light source that emits radiation corresponding to the sensitivity wavelength of the photosensitive material can be used as the illumination or writing light source. Natural light, (sunlight), incandescent lamps, halogen-filled lamps, mercury vapor lamps, fluorescent lamps, and flash light sources such as strobes or metal-fired flashbulbs are common.

Gaseous, dye solution or semiconductor lasers, light emitting diodes, and plasma light sources emitting light in the wavelength range from ultraviolet to infrared can also be used as recording light sources. In addition, rays are applied to microshutter arrays using fluorescent surfaces (such as CRT), liquid crystals (LCD), and lead titanium zirconate (PLZT) doped with lanthanum, which are emitted from phosphors excited by electron beams. It is also possible to use an exposure means that combines a shaped or planar light source.

If necessary, the spectral distribution used for exposure can be adjusted using color filters.

The color developing solution used in the development of the light-sensitive material of the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine color developing agent as a main component. As this color developing agent, aminophenol compounds are also useful, but p-phenylenediamine compounds are preferably used, representative examples of which are 3-methyl-4-amino-NN-diethylaniline, 3-methyl-4- Amino-N-ethyl-N-β-
Hydroxylethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-N-β
-methoxyethylaniline and their sulfates, hydrochlorides, p-toluenesulfonates, and the like. These diamines are generally more stable in their salt form than in their free state, and are therefore preferably used.

Color development agents include pH buffering agents such as alkali metal carbonates, borates or phosphates, development inhibitors or antifoggants such as bromides, iodides, penzimidazoles, penzothiazoles or merkabut compounds. Generally, it contains agents such as agents. Also, if necessary, preservatives such as hydroxylamines, dialkylhydroxylamines, hydrazines, triethanolamine, triethylenediamine or sulfites, organic solvents such as triethanolamine, diethylene glycol, benyl alcohol, etc. , development accelerators such as polyethylene glycol, quaternary ammonium salts, amines, dye-forming couplers, competitive couplers, nucleating agents such as sodium boron hytride, auxiliary developers such as 1-phenyl-3-virazolidone, Viscosifying agents, various chelating agents such as aminopolycarboxylic acids, aminopolyphosphonic acids, alkylphosphonic acids, and phosphonocarboxylic acids, and antioxidants described in OLS No. 2,622,950. A coloring agent or the like may be added to the color developing solution.

In the development process for reversal color photosensitive materials, black and white development is usually performed followed by color development. This black and white developer includes dihydroxybenzenes such as hydroquinone, 3-pyrazolidones such as 1-phenyl-3-pyrazolidone, or N-
Known black and white developers such as aminophenols such as methyl-p-aminophenol can be used alone or in combination.

Not only a color developing solution but also any photographic developing method may be applied to the light-sensitive material of the present invention. The developing agents used in the developer include dihydroxybenzene-based developing agents, ■-
There are phenyl-3-virazolidone-based developing agents, p-aminophenol-based developing agents, etc., and these can be used alone or in combination (for example, l-phenyl-3-vilapridones and dihydroquinebenzenes, or p-aminophenols and dihydroquinebenzenes). benzenes) can be used. The light-sensitive material of the present invention may also be processed with a so-called infectious developer using a sulfite ion buffer such as carbonyl bisulfite and hydroquinone.

In the above, examples of the dihydroxybenzene-based developing agent include hydroquinone, chlorohydroquinone, promohydroquinone, isopropylhydroquinone, toluhydrohydroquinone, methylhydroquinone, 2,
There are 3-dichlorohydroquinone, 2,5-dimethylhydroquinone, etc., and 1-phenyl-3-virazolidone type developing agents include 1-phenyl-3-virazolidone,
4,4-dimethyl-1-phenyl-3-virazolidone,
4-hydroxymethyl-4-methyl-1-phenyl-3
p-aminephenol developing agents include p-aminephenol, N-
Methyl-p-aminophenol or the like is used.

A compound that provides free sulfite ions, such as sodium sulfite, potassium sulfite, potassium metabisulfite, and sodium bisulfite, is added to the developer as a preservative. In the case of an infectious developer, sodium formaldehyde bisulfite, which provides almost no free sulfite ions in the developer, may be used.

As the alkaline agent for the developer used in the present invention, potassium hydroxide, sodium hydroxide, potassium carbonate, sodium carbonate, sodium acetate, tribasic potassium phosphate, diethanolamine, triethanolamine, etc. are used. The pH of the developer is usually set to 9 or higher, preferably 9.7 or higher.

The developer solution may also contain organic compounds known as antifoggants or development inhibitors. Examples include azoles such as henzothiazolium salts, nitroindazoles, nitropenzimidazoles, chlorohenzimidazoles, promobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, Aminotriazoles, henzotriazoles, nitropenzotriazoles, mercaptotetrazoles (especially l-phenyl-5-mercaptotetrazole), etc.; mercaptopyrimidines; mercaptotriazines: thioketo compounds such as oxazolinthione; asaindenes, e.g. Triaçaindenes, tetraaçaindenes (especially 4-hydroxy-substituted (1,
3. (3a, 7) tetrazaindenes), pentaazaindenes, etc.; benzenethiosulfonic acid, benzenesulfinic acid, benzenesulfonic acid amide, sodium 2-mercaptobenzimidazole-5-sulfonate, and the like.

The developer that can be used in the present invention may contain the same polyalkylene oxide as described above as a development inhibitor. For example, polyethylene oxide having a molecular weight of 1000 to 10000 may be contained in an amount of 0.1 to 10 g/A'.

It is preferable to add nitrilotriacetic acid, ethylenecyaminetetraacetein azide, triethylenetetraamine, xaacetic and, diethylenetetraamine pentaacetek azide F, etc. as a water softener to the developer that can be used in the present invention. .

The developer used in the present invention includes a compound described in JP-A No. 56-24347 as a silver stain prevention agent, a compound described in JP-A-62-212651 as an agent for preventing uneven development,
As a solubilizing agent, the compounds described in Japanese Patent Application No. 60109743 can be used.

In the developing solution used in the present invention, a buffering agent is added.
Boric acid described in 1-28708, JP-A-6-0-9-3
4 3 Saccharides (e.g. sutucarose), oximes (e.g. acetoxime), phenols (e.g.
For example, 5-sulfosalicylic acid), tertiary phosphates (eg, sodium salt, potassium salt), etc. are used.

Various compounds may be used as the development accelerator used in the present invention, and these compounds may be added to either the sensitive material or the processing solution.

Preferred development accelerators include amine compounds, imidazole compounds, imidazoline compounds, phosphonium compounds, sulfonium compounds, hydrazine compounds,
Examples include thioether compounds, thione compounds, certain mercapto compounds, isoion compounds, and thiocyanates.

This is especially necessary for rapid development processing in a short period of time. It is desirable to add these development accelerators to the color developing solution, but depending on the type of accelerator or the position on the support of the photosensitive layer to be accelerated, it may be added to the photosensitive material. can. It can also be added to both the color developing solution and the photosensitive material. Furthermore, depending on the case, a pre-bath for the color developing bath may be provided and the additive may be added therein.

Amine compounds useful as amino compounds include both inorganic amines and organic amines, such as hydroxylamine. Organic amines can be aliphatic amines, aromatic amines, cyclic amines, aliphatic monoaromatic mixed amines or heterocyclic amines; primary, secondary and tertiary amines as well as quaternary ammonium compounds are all useful. be.

After color development, the photographic emulsion layer is usually bleached.

The bleaching process may be performed simultaneously with the fixing process, or may be performed separately. Furthermore, in order to speed up the processing, a bleach-fixing treatment may be performed after the bleaching treatment. Examples of bleaching agents include iron (■), cobalt (■), and chromium (■).
), compounds of polyvalent metals such as copper (II), peracids, quinones, nitrone compounds, etc. are used. Typical bleaching agents include ferricyanide: dichromate; iron(III)
Or organic complex salts of cobalt (I[I), such as aminopolycarboxylic acids such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, nitrilotriacetic acid, l,3-cyamino-2-propanoltetraacetic acid, or citric acid, tartaric acid, malic acid, etc. Complex salts of organic acids; persulfates,
Mancanate; nitrosophenol, etc. can be used. Of these, iron(II) ethylenediaminetetraacetate
I) salts, cyethylenetriaminepentaacetic acid iron (I) salts and persulfates are preferred from the viewpoint of rapid processing and environmental contamination. Furthermore, the ethylenecyaminetetraacetic acid iron(III) complex is particularly useful in both stand-alone bleach and single bath bleach-fix solutions.

A bleach accelerator may be used in the bleaching solution, bleach-fixing solution, and their prebaths, if necessary.

Specific examples of useful bleach accelerators are described in the following specification: U.S. Patent No. 3,893,858, West German Patent No. 1
, No. 290,812, No. 2,059,988, JP-A-5-3-3-2-7-3-6, No. 5357-831,
37418, 5 3-6 5 732, 51
-72623, 5 3-9 5 630, 5
3-9 5 6 3 1, 51104232, 5 3-1 2 4 4 2 4, 53-1416
No. 23, No. 5 3-2 8 4 2 6, Research
Disc Rocher No. 1 7 1 2 9 (19
Compounds having a mercapto group or cisulfide group, such as those described in Japanese Patent Publication No. 1978-140129 (Japanese Patent Publication No. 1987-140129)
No. 506, JP-A No. 51-20 832, JP-A No. 53-3
2 7 3 5, thiourea derivatives described in U.S. Pat. No. 3,706,561; West German Patent No. 1,127,71
No. 5, iodide described in Japanese Patent Publication No. 58-16235; polyethylene oxide products described in West German Patent No. 966,410 and West German Patent No. 2,748.430, Japanese Patent Publication No. 1984 5-8
Polyamine compound described in No. 8 3 6; other JP-A No. 49-42434, No. 49-59644, No. 539
No. 4927, No. 5 4-3 5 7 2 7, No. 55
Compounds described in No. 26506 and No. 58-163940 and iodine and bromine ions can also be used.

Among these, compounds having a mercapto group or a disulfide group are preferred from the viewpoint of a large promoting effect, and are particularly preferred, as described in U.S. Patent No. 3,893,858 and West German Patent No. 1,290,81.
No. 2 and JP-A-51-95630 are preferred. Furthermore, compounds described in US Pat. No. 4,552,834 are also preferred.

These bleach accelerators may be added to the photosensitive material.

These bleach accelerators are particularly effective when bleach-fixing color light-sensitive materials for photography.

Examples of the fixing agent include thiosulfates, thiocyanates, thioureas of thioether compounds, and a large amount of iodides, but thiosulfates are generally used. As the preservative for the bleach-fix solution and the fix solution, sulfites, bisulfites, or carbonyl bisulfite adducts are preferred.

After the bleach-fixing treatment or the fixing treatment, washing treatment and stabilization treatment are usually performed. Various known compounds may be added to the water washing process and stabilization process for the purpose of preventing precipitation and saving water. For example, in order to prevent sedimentation, water softeners such as inorganic phosphoric acid, aminopolycarboxylic acid, organic aminopolyphosphonic acid, and organic phosphoric acid, as well as disinfectants and anti-piping agents that prevent the growth of various bacteria, algae, and phlegm, are recommended. Agents, metal salts such as magnesium salts and aluminum salts and bismuth salts, surfactants for preventing drying load and unevenness, and various hardening agents may be added as necessary. Or L.E. We
st,' Photo. Sci. Eng. ), 6th
Compounds described in Vol., pp. 344-359 (1965) may be added. It is particularly effective to add chelating agents and anti-high agents.

In the washing process, two or more tanks are generally washed in countercurrent water to conserve water. Furthermore, instead of the water washing process,
A multi-stage countercurrent stabilization treatment process as described in No. 7-8 5 4 3 may also be carried out. In the case of this step, 2 to 9 countercurrent baths are required. In addition to the above-mentioned additives, various compounds are added to this stabilizing bath for the purpose of stabilizing images. Various buffers (e.g. borate, metaborate, borax,
Representative examples include phosphates, carbonates, potassium hydroxide, sodium hydroxide, aqueous ammonia, monocarboxylic acids, dicarboxylic acids, polycarboxylic acids, etc.) and aldehydes such as formalin. others,
Chelating agents (inorganic phosphoric acid, aminopolycarboxylic acid, organic phosphoric acid, organic phosphonic acid, aminopolyphosphonic acid, phosphonocarboxylic acid, etc.), fungicides (penzisothiazolinone, irithiazolone, 4-thiazoline, etc.) as necessary. Various additives such as benzimidazoles, halogenated phenols, sulfanilamides, penzotriazole, etc.), surfactants, fluorescent brighteners, hardeners, etc. may be used, and two compounds for the same or different purposes may be used. More than one species may be used in combination.

In addition, ammonium chloride,
It is preferable to add various ammonium salts such as ammonium nitrate, ammonium sulfate, ammonium phosphate, ammonium sulfite, and ammonium thiosulfate.

Furthermore, in the case of color photosensitive materials for photography, the normally performed post-fixing, water-washing, stabilization) process can be replaced with the above-mentioned stabilization process and water-washing process (water-saving treatment). At this time, if the macenta coupler is 2 equivalents, formalin in the stabilizing bath may be removed.

The washing and stabilization processing time of the present invention varies depending on the type of sensitive material and processing conditions, but is usually 20 seconds to 10 minutes, preferably 20 seconds to 5 minutes.

The silver halide color light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and speeding up processing. For this purpose, it is preferable to use various precursors of color developing agents.

For example, indoaniline compounds described in US Pat. No. 3,342,597, US Pat. No. 3,342,599, Research Disclosure No. 14850 and US Pat. No. 15159
The Schiff base type compound described in No. 13924, the andole compound described in U.S. Patent No. 13924, the metal salt complex described in U.S. Pat. Kaisho 5 6-6 2
3 No. 5, No. 56-16133, No. 5 6-5 9
2 3 No. 2, No. 56-67842, No. 56-83
No. 734, No. 56-83735, No. 56-83736
No. 5 6-8 9 7 3 5, No. 56-818
No. 37, No. 5 6-5 4 4 30, No. 56-1
No. 06241, No. 56-107236, No. 57-97
Examples include various salt-type precursors described in No. 531 and No. 57-83565.

The silver halide color light-sensitive material of the present invention may contain various l-phenyl-3-virazolidones, if necessary, for the purpose of promoting color development. Typical compounds are disclosed in JP-A-56-64339 and JP-A No. 57-14.
No. 4547, No. 57-21.1147, No. 5115
0 5 3 No. 2, 5L-50536, 5 8-
50533, 513-50534,
It is described in No. 58-50535 and No. 58-■15438.

Various treatment liquids in the present invention are used at 10°C to 50°C. A temperature of 33°C to 38°C is standard, but higher temperatures can be used to accelerate processing and shorten processing time, or lower temperatures can be used to improve image quality and stability of the processing solution. I can do it. Further, in order to save silver on the photosensitive material, a treatment using cobalt intensification or hydrogen peroxide intensification as described in German Patent No. 2,226,770 or US Pat. No. 3,674,499 may be carried out.

A heater, a temperature sensor, a liquid level sensor, a circulation pump, a filter, a floating pig, a squishy, etc. may be provided in each of the processing baths as necessary.

Further, during continuous processing, a constant finish can be obtained by using a replenisher for each processing solution to prevent fluctuations in the solution composition. The replenishment amount can be reduced to half or less than the standard replenishment amount to reduce costs.

When the light-sensitive material of the present invention is a color paper, standard fixing processing can be carried out very generally, and also when it is a color photographic material for photographing, as required.

(Example) Next, the present invention will be explained in more detail based on examples.

Example 1 (Preparation of Emulsion A) An aqueous solution of silver nitrate and 0.0% silver/mole. ! x/0-4 mol of ammonium rhodium(III') hexachloride was added to the sodium chloride aqueous solution at 3!0C using the double jet method.
pH in gelatin solution of 6,! A monodisperse silver chloride emulsion with an average grain size of 0.07 μm was prepared by mixing while controlling the mixture so that the following was achieved.

After particle formation, soluble salts were removed by a seven-part curation method well known in the art, and l-hydroxy-6-methyl-7,3,3a,7-tetraazaindene and l-phenyl were added as stabilizers. ! - Added mercabutotetrazole. Ze2tin contained in emulsion/kg! jg1 silver was / 01g. (Emulsion A) (Principles of light-sensitive material) Add the following nucleating agent and nucleation accelerator to the emulsion A,
Next, polyethyl acrylate latex (3oθmg
/m2), and a hardening agent and Li. 2. J-dichloro-bu-hydroxy/,3,j-triazine sodium salt was added at a rate of 3. ! A silver halide emulsion layer was coated on a polyethylene terephthalate transparent support so that the amount of silver was 1.5 g, and gelatin (/.J
g/m2), compound of the present invention ■-7 (0.
/ 2 g/m 2 ”), a protective layer containing the following three surfactants, a stabilizer, a button and a matting agent as coating aids was applied and dried.

(Sample/) Nucleating agent addition t (mg/m2) Surfactant addition amount (mg/m2) C}{2COOC6Hl3 CHCOOC 6H13 SO3Na 3 7 Stabilizer thioctic acid 6. 0 Matting agent polymethyl methacrylate (average particle size 3.!μ) jO. A dispersion of the compound I-7#'i of the present invention having a concentration of 0 mg/m2 was prepared and used according to the following procedure.

(Preparation of dye dispersion) ■Liquid/Dye (Compound I-7 of the present invention) 2 4
Solution I was added little by little while stirring Solution ■ at 7 g ψ o 'C.

(Creation of Comparative Sample) l) A sample was prepared using the following dye instead of Compound 1-7 in Example/ (Comparative Sample l-A) (0.07!g/m2) 2) Example l The following dye was used in place of compound I-7. (Comparative sample/-B) This dye is exemplified by worr7oψ7taψ.

CH3 0. /g/m2 3) A comparative sample /-C was prepared using the following protective layer instead of the protective layer containing the compound 1-7 of the present invention in Example 11.

Acid-treated gelatin Og/m2 mordant CH3 l. θg/mz dye O 7! g/m 2 Surfactant■ C11H23CONH(CH2)3N(CH3')2
(0{2)4S03eO . j j g / m 2 CH2COOC,H13 CHCOOC6H13 0 . 0377m2 SO3Na C8F17. SO2NCH2COOK O. 002j/m2 C3H7 Stabilizer Thioctic acid O. θ04/m2 Matting agent polymethyl methacrylate (average particle size s.zp”) o.oota/m2 (performance evaluation) (1) The above ← samples were printed using a Dainippon Screen Seimei-shitsu printer P-407. The film was exposed to light through an optical wedge, developed with the following developer at 3!r 0C for 20 seconds, fixed in a conventional manner, washed with water, and dried.

Basic formulation of developer Hydroquinone Jj. OgN-methyl-p-amino 7enol//2sulfate 0. Ig sodium hydroxide/J. Og tribasic potassium phosphate 71A. Og potassium sulfite
fO. Og ethylenediaminetetraacetic acid tetrasodium salt l・θg potassium bromide Tei. Og! -Methylbenzotriazole 0.4g 3-diethylaminol
．． Co-propanediol /! ．． Add Og water and adjust II (pH=//
．． r) As a result, Example/December and Comparative Sample/-A were completely bleached, but Comparative Samples i-B and l10 remained with yellow stains. Comparative sample i-B was completely decolored when the development time was increased for 30 seconds in the housing. As described above, the compounds of the present invention are rapidly processed and decolorized.

(2) Test of Tone Variability The two samples described above were exposed to light through a flat screen using the printer described above, and were otherwise developed in the same manner as in the test for t'i (1). After determining the exposure time for each sample to return the halftone dot area to l:l, the halftone dot area is I looked into how much it would expand. The larger the magnification, the better the tone variability. The results are shown in Table 1. As can be seen from Table 1,
Comparative sample /-A has significantly reduced tone variability, whereas sample I of the present invention has high tone variability. This is because the dye used in Comparative Sample/1A is water-soluble and diffusible, so it is uniformly diffused in the photosensitive emulsion layer 1 from the layer added during storage. This is because even if the number of dots was increased, the expansion of the halftone dot area was suppressed due to the irradiation prevention effect of the dye. On the other hand, compound I-7 of the present invention exhibits high tone variability since it is fixed in the added layer.

Comparative samples I-B and/-C also showed good tone variability.

Table 1/ Tone variability (indicated by increase in halftone dot area) (3)
Evaluation of contamination (stain) by reducing fluid The strips of the sample of the present invention and the sample of the comparative example obtained by processing in (2) above were added to the following 7 Armor reducing fluid at 2oC for 10
It was immersed for a second, washed with water, and dried. As a result, the halftone dot area of all the samples was reduced to about 33%, but in comparison sample /-C, severe brown staining occurred over the entire surface. No stain Fi was observed in the sample buttons of the present invention and comparative samples /-A and /-B.

7 armor reduction fluid When using, liquid I: liquid J: water =/00@:j part:/Oθ part Mix with

As described above, the samples of the present invention were good in terms of decolorization, tone changeability, shrinkage, and force reduction properties.

EXAMPLE Paper support samples A1B and C were prepared using a gelatin undercoat layer and a dye dispersion below the housing cover after corona discharge treatment on a paper support laminated on both sides with copolyethylene.

Dye Dispersion Method The following dye crystals were kneaded and made into fine particles using a sand mill. Furthermore, 0.jg of citric acid was dissolved/0%
Lime-treated gelatin aqueous solution 2! The sand used in the dispersion in rrJ was removed using a glass filter, and the dye adhering to the sand on the glass filter was further removed to obtain a 7-polygelatin solution/00ml. (The average particle size of the dye particles is O
．． /! It was μm. ) Compound of the present invention ■-7 ...... l. θ
g Compound I-3 of the present invention/.../. A
j% aqueous solution of g rml and compound 1-33 of the present invention/. 1, g and ■2ψ / .
6g was prepared in the same manner.

Paper support A Undercoat layer gelatin o, x g/m
2 Paper support B Antihalation layer gelatin O.zg/m2 Compound of the present invention 1 7 jj mg/m2 Compound of the present invention I-3/ψO m g/m 2 Paper support C Antihalation layer Gelatin 0. 4 g/
m 2 Compound of the present invention 1 - j j 41 0
mg/m2 Compound of the invention [-244
4t (7 mg/m2) On paper support samples A, B> and C, multilayer color photographic paper samples COL 1 to COL φ having the layer structure shown below were obtained.

The coating solution was prepared as follows.

First layer coating solution preparation Yellow coupler (ExY)/5'. /g and color image stabilizer (Cpd-/) 4t. 44g and color image stabilizer (Cp
d-7)/. 7. μg of ethyl acetate. CC button and solvent (8o1v-/)r. Add Jg and dissolve, and this solution
/ 0'A Sodium dodecylbenzenesulfonate I
Contains ce/014 gelatin aqueous solution/I j cc
It was emulsified and dispersed. On the other hand, silver chlorobromide emulsions (cubic, with an average grain size of 0.r J' pm and 0.70 pm)
(silver molar ratio). Coefficient of variation of particle size distributionVio. or and O. IO, each emulsion contains 0.2 mole of silver bromide locally on the grain surface) and the following blue-sensitive sensitizing dye per mole of silver for dog-sized emulsions:
Add 2.0x/0-4 mol each, and 2.0x/0-4 mol each for small size emulsions. A sample was prepared in which sulfur sensitization was performed after adding j×/0−4 mol. The above emulsified dispersion and this emulsion were mixed and dissolved to prepare a first coating solution having the following composition.

Coating solutions for the second to seventh layers were also prepared in the same manner as the first layer coating solution. As the gelatin hardening agent for each layer, /-oxy-J,j-dichloro-S-triazine sodium salt was used.

The following was used as a spectral sensitizing dye for each eyebrow.

Blue sensitive emulsion layer (2.OX/0-4 mole each for dog size emulsions and A.!XIO-4 mole each for small size emulsions per silver halide/mole) green sensitive emulsion layer (per mol of silver halide, ψ.Ox/0-4 mol for large size emulsions, j,l for small size emulsions)
, x/0 4 mol) (per mol of silver halide, 7.0 x IO-5 mol for large size emulsions, / for small size emulsions with holes)
．． OX/0-5 mole) Red-sensitive emulsion layer C2H5 1eC5H11 (per mole of silver halide, 1,C per mole of large size emulsion)
For small size emulsions with F'10.2x/0-4 mol%1, i. For the red-sensitive emulsion layer, the following compounds were added at J. AX/O-3 moles were added.

For the blue-sensitive emulsion layer, green-sensitive emulsion layer, and red-sensitive emulsion layer, l-(!-methylureidophenyl)! - Mercaptotetrazole per silver halide/mole, respectively! r
．． ! ×/0-5 mol 7.7×/0-4 mol, 2,jX
/0-4 mol was added.

1. For the blue-sensitive emulsion layer and the green-sensitive emulsion layer, φ-hydroxy-6-methyA/-/,J,3a,7-tetrazaindene was added per silver halide/mole, respectively.
x/0-4 mol and 2 x/0-4 mol were added.

One paper support sample A had the following comparative dyes added to its emulsion layer.

fmg/m2 Kayobi J! mg/m2 (layer structure) The composition of each layer is shown below. The numbers represent the coating amount (g/m2). The silver halide emulsion represents the coated amount in terms of silver.

Support: Polyethylene laminated paper [first layer side polyethylene contains white pigment (Ti02) and bluish dye (ulmarine blue)] with undercoat layer and antihalation layer Sample A% A% B, C φ type No. Single layer (blue sensitive layer) Silver chlorobromide emulsion 0.30 gelatin/. rbu yellow coupler (ExY) 0. r2 color image stabilizer (Cpd-
/) θ. /2 solvent (Solv-/)
0. Jj color image stabilizer (Cpd-7)
θ． ot Second layer (color mixing prevention layer) Gelatin θ, 7 Color mixing prevention agent (Cpd-j) o. or solvent (8o1v
-/) 0,/& solvent (Solv-4C
) 0.01 Third layer (green sensitive layer) Silver chlorobromide emulsion (cubic, 1:3 mixture (Ag molar ratio) of one with an average grain size of 0.!!! μm and one with an average grain size of 0.32 μm. Grains Coefficient of variation of size distribution pO./0 and o.o
r, each emulsion contained AgBrO. o. ixze 2
Chin l. φ magenta coupler (ExM) 0. CO color image stabilizer (CPCT)
-ko) 0. Oj color image stabilizer (Cpd-j)
o. iz color image stabilizer (Cpd-4)
o,o two-color image stabilizer (Cpd-1)
o,os solvent (SOIV-2) 0
．． 4tO fourth layer (ultraviolet absorption layer) Gelatin /. ! t Ultraviolet absorber (UV-/) o. μ7 color mixing prevention agent (
Cpd-t) 0.0! Solvent (8o1v-t
) o. xa Fifth eyebrow (red sensitive layer) Silver chlorobromide emulsion (cubic, l:l mixture (Ag molar ratio) of one with an average grain size of θ.!tμm and one of O.ψ!μm. Grain size distribution The coefficient of variation Vi0.09 and 0.
//, each emulsion contained kg BrO, A mole locally on a part of the grain surface) 0.23 gelatin/. j41 (Cyan coupler (ExC) 0.J color image stabilizer (Cpd-4) 0,/7 color image stabilizer (Cp
d-7) 0. Color image stabilizer (Cpd-r
) 0.0ψ Solvent (Solv-A)
0,/j Sixth layer (ultraviolet absorbing layer) Gelatin ultraviolet absorber (UV-7) Color mixing inhibitor (Cpd-,?) Solvent (Solv-j) Seventh layer (protective layer) Gelatin polyvinyl alcohol scum (denatured) 77%) liquid paraffin. ! 3. /4. θko. Ot7. 3 3 Lyle modified copolymer 0. /7 0.03 (ExY) l of yellow coupler: l mixture (molar ratio) (ExM) l of magenta coupler: l mixture (molar ratio) (ExC) shear/coupler α R=C2H5 and C4H9 and α Mixture of coa:a (Cpd l) Color image stabilizer ((cpa Co) Color image stabilizer (Cpd 3) Color image stabilizer Cpd ψ) Color image stabilizer (Cpd-1) Color mixing inhibitor OH (cpa-+) 14t l mixture of color image stabilizers (weight ratio) (Cpd-7) Color image stabilizer average molecular weight 40,000 (Cpd-1) Color image stabilizer OH (JM (cpd ta) Color image stabilizer Agent (UV-/) 41-: mixture of ultraviolet absorber (weight ratio) (Solv-i) Solvent (Sol v-2) 2: l mixture of solvent (volume ratio) (Solv-g) Solvent (So I V-!) Solvent Cα) C8H17 1 (CH2) s i Cα) C8Hl7 (So 1 ■-6) Regarding the sample λ-/Ko ψ in which the solvent was observed, a sensitometer (manufactured by Fuji Photo Film ■, FWH type, Color temperature of light source 3,0
o 0K) to provide stepwise exposure for sensitometry through blue, green, and red filters. On the other hand, exposure was performed to measure resolution (CTF), and then the following processing steps were performed. The concentration of the observed sample was measured and the results shown in Table 1 were obtained.

color development bleach fixing Rinse ■ Rinse ■ Rinse ■ drying drying 3! 0C 30~3!0C 30~3!0C 3θ~3!0C 30~3!0C 7o~to’c <Lt seconds/bu/m! ! ψ! seconds ko/jml 2 theta seconds λθ seconds 20 seconds 3! θmJ 60 seconds /71 /71 /Ol ion /Di *Replenishment amount is per 1m2 of photosensitive material (A 3-tank countercurrent flow system was used for rinsing ■→■.

The composition of each treatment liquid is as follows.

) Water Ethylenediamine-N,N,N,N- Tetramethylenephosphonic acid Potassium bromide Triethanolami Sodium chloride Potassium carbonate N-Ethyl-N-(β-methanesulfonamidoethyl) -3-Methyl-← -Aminoaniline sulfate N ,N-bis(cal/.!g θ.0/!g n ;r.Og l .gg ko!g room ! ・Og f00mll ko・Og /2.Og kojg 7 ・Og boxymethyl)hydrazine j . ! g7,
Og optical brightener (WHITEX Add water /000ml /000mlp
H(x.t'c) /o. or io. az bleach-fix solution (tank solution and refill solution are the same) water
00ml ammonium theosulfate (70%) /oomij sodium sulfite /7g iron ethylenediaminetetraacetate (I[[) ammonium! jgDisodium ethylenediaminetetraacetic acid jgAdd water /θ00mijpH(λj
0c) t. o Rinse solution (tank solution and replenishment solution are the same) Ion exchange water (calcium and magnesium are each jpp)
When the dye according to the present invention is used in an antihalation layer, the resolution can be significantly improved with a relatively small decrease in g and no noticeable residual color. Furthermore, by using dyes (I) and (II) of the present invention in combination, resolution can be significantly improved in all the cyan, magenta, and yellow regions.

Example 3 Preparation of dye fixed layer A transparent PET support with a thickness of 0.0 pm was used as the support. In order to improve the adhesion with the hydrophilic colloid layer, the surface of the support was previously subjected to corona discharge treatment, and then a first undercoat layer made of styrene-butadiene latex was applied, and the upper layer was coated with gelatin O. A second undercoat eyebrow of Org7m2 was provided.

A fine dispersion of the dye was coated on this support as a gelatin dispersion solution in the coating amount shown below. In this way, the anti-ration layer was manufactured as y4.

●Gelatin/． rg/m2・Dye Dyes and amounts listed in Table 3 ● Potassium polystyrene sulfonate (average molecular weight 600,000)! ! mg/rn2/O
mg/m2 ●Phenoxyethanol/. rmg/m
2●l. +2-bis(sulfonylacetamido)ethane/00mg/rn2 Preparation of emulsion coating solution The raw milk NALFi shown below is a surface latent image type emulsion, and negative-tone characteristics can be obtained using a commercially available microfilm general-purpose processing solution. Further, by performing reversal processing using a reversal processing liquid, positive type characteristics can be obtained.

<Preparation of raw emulsion na/> Solution (7 rac x io-3 g (Solution ■ 3! 0C Solution ■ 3! 0C Solution ■ Add Solution ■ and Solution ■ to Solution I stirred well at room temperature at the same time for ! minutes. When the entire amount of solution (1) was added, a cubic monodisperse emulsion with an average grain size of 0.2 rpm was finally obtained.

At this time, the addition rate of solution (2) is such that the pAg value in the mixing container is always 7. ．． It was added while adjusting the amount to be IO. Note that solution ■ starts 7 minutes after the start of addition of solution ■! Added over a period of minutes. After adding solution ■, wash with water and desalinate using the sedimentation method, and add inert gelatin/
It was dispersed in an aqueous solution containing 00 g. To this emulsion, sodium thiosulfate and chlorauric acid q hydrate were added in amounts of 3 to 3 ml per mole of silver. mg each, and the pH and pAg values were adjusted to r.
After adjusting to 2 and 7.0 (gθ'c), t at 7!0C.
A chemical sensitization treatment was performed for 0 minutes to obtain a surface latent image type silver halide emulsion.

The layer structure and group precepts for each layer are as follows.

The emulsion layer, surface protection layer, conductive layer, and gel layer other than the antinolation layer were prepared and coated in the following coating amounts to obtain a photographic material.

<Protective layer><Emulsionlayer> Rium 3 j Sensitizing dye (compound ■) C2H5 I <Back conductive layer> Rium (Gel layer) 7 Coating amount mg/m2 Inert gelatin/ 610 Sodium dihexyl α-sulfosuccinate 3 ← Processing method Reversal development processing Reversal development processing is performed using a FIOR deep tank automatic developing machine manufactured by Alien Products, Inc., USA, and a commercially available reversal processing solution (FRj3 manufactured by FR Chemicals, Inc., USA)
/,jJko,jJ3,jJlt,! ．． ! j) under the following conditions.

Negative development processing Negative development processing was performed using a commercially available general-purpose microfilm processing solution (FR-337 developer manufactured by FR Chemicals, USA) using an F-/O deep tank automatic developing machine manufactured by Alien Products, Inc., as follows. I went with the conditions.

Evaluation of sharpness Sharpness was evaluated by t-1MTF. MTF photographic materials
Exposure to white light using a measuring wedge for l/lOθ seconds,
The automatic processor treatment described above was carried out.

The MTF was measured with an aperture of φ00×2 μm2, and the optical density was calculated using the MTF value at a spatial frequency of 20 cycles/mm. Evaluation was made in the 0 part.

The results are shown in Table-3.

(2) Evaluation of residual color After the unexposed film was subjected to the automatic development process described above, it was passed through a Macbeth Status A filter and the green transmission density and blue transmission density were measured.

The results are shown in Table-3.

As is clear from Table 3, it can be seen that according to the present invention, a photosensitive material with excellent sharpness and residual color can be obtained.

Example 1g The same solution used in the preparation of raw emulsion +l in Example 3 was used. However, the following points are different.

For solution ■, solution ■ and solution ■! They were simultaneously added for 1 minute, and when octahedral particles with an average particle size of θ, io μm were formed, the addition of liquids ① and ① was temporarily stopped, and per mol of silver,
Sodium thiosulfate and chloroauric acid tetrahydrate respectively II
jmg was added at a time, followed by chemical sensitization treatment at 7j0C for zO minutes.

Simultaneous addition of solution ■ and solution ■ to the chemically sensitized core particles thus obtained is continued again, and the addition of solution ■ is resumed! ■ Solution after a minute! The pAg value of the mixture was 7. ! θ
7!0C while adjusting the addition rate of the liquid so that
Then, the entire amount of solution (■) was added over UO minutes. In this way, a cubic core/shell emulsion with an average grain size of 09×r μm was finally obtained. The operations after water washing and desalting are exactly the same as for raw milk Φl.

In this way, an internal latent image type cubic core/shell emulsion whose surface was chemically sensitized was obtained. ← Raw milk ◆ C) The raw emulsion of φ is a so-called core/shell type internal latent image emulsion, and in combination with a nucleating agent, a positive image can be obtained directly with a single development using a general-purpose microfilm processing solution. It is something that can be done.

Photographs were prepared in the same manner as in Example 3, except that the following nucleating agent (compound ■) was added to prepare the emulsion layer in Example 3 so that the coating amount was 3 g/m2. I got the material.

Nucleating agent (compound ■) 10 Ro2C=α Evaluation of sharpness was performed in the same manner as in Example-3.

For evaluation of residual color, a film exposed to obtain Dmin was used instead of the unexposed film used in Example-3. The rest was carried out in the same manner as in Example-3.

The development process was carried out in the same manner as the negative development process in Example-3.

table As is clear from the graph, according to the present invention, Sharp Every time, It can be seen that a photosensitive material with excellent residual color can be obtained.

Claims (2)

[Claims] (1) A silver halide photographic material comprising a hydrophilic colloid layer containing at least one compound represented by the following general formula (I) as a solid fine particle dispersion. General formula (I) ▲ Numerical formulas, chemical formulas, tables, etc. Represents an amino group, L_
1, L_2, and L_3 each represent a methine group, and n represents 0 or 1. However, the compound represented by general formula (I) has at least one carboxyl group, sulfonic acid arylamide group, or phenolic hydroxyl group in the molecule. ) (2) Contains at least one compound represented by the general formula (I) as solid-dispersed fine particles, and contains the following general formula (I)
A silver halide photographic material comprising at least one of the compounds represented by I) as solid-dispersed fine particles. General formula (II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R_5 is a hydrogen atom, an alkyl group, an aryl group,
Cyano group, hydroxyl group, -COOR_7, -CONR_7R
_8, -OR_7, -NHCOR_7, and R_6 represents an alkyl group and an aryl group, respectively. L_1_1, L
_1_2, L_1_3, L_1_4, and L_1_5 each represent a methine group, and p and q represent 0 or 1. however,
The compound represented by general formula (II) has at least one carboxyl group, sulfonic acid arylamide group, or phenolic hydroxyl group in the molecule. )